Liquid germicidal compositions



Patented Sept. 26, 1944 2,359,241 LIQUID GERMICIDAL COMPOSITIONSAlexander M. Partansky, Midland, Mich., assignor to The Dow Chemi Mich.,a corporation cal Company, Midland, 1 Michigan No Drawing. ApplicationJuly 31, 1942, Serial No. 453,031

8 Claims.

This invention relates to antiseptics and to ermicides, and isparticularly concerned with an improved water-miscible germicidalconcentrate comprisin orthophenylphenol a the principal toxicingredient.

Orthophenylphenol and its salts are well known as bactericides. Thesecompounds are employed in the form of dispersions, solutions, emulsions,and the like, with water, organic solvents, soaps, and oils wherever amild germicide is required which is substantially non-toxic to humans.

Orthophenylphenol, per se, is substantially water-insoluble and isgenerally employed in combination with alkali, soaps, water-miscibleorganic solvents, and synthetic organic emulsifying and detergent agentsin order that aqueous dispersions thereof may be-obtained. A limitationon the use of such mixtures resides in the fact that dilutions thereoffrequently are not as effective as is desirable for an all-purposegermicide. When soaps and wetting agents are employed, the germicidaleffectiveness of diluted compositions is frequently lower than mightreasonably be anticipated from a knowledge of the toxicitycharacteristics of the pure orthophenylphenol compound.

' terpineol. Improved compositions are thereby 0b- A furtherdisadvantage in the use of ortho- I phenylphenol containing compositionsresides in their comparatively low effectiveness against Staphylococcusorganisms. Thus, while many of the water-miscible concentratescomprising orthophenylphenol as the principal toxic ingredient give asatisfactory kill against such organisms as E'. typhi, few, if any, havea corresponding action against Staph. aureus.

Pine oil has been used as a constituent of germicidal compositions incombination with phenolic derivatives. Here again compositions areobtained which give a satisfactory control of some organisms, but whichfor the most part are not satisfactory for the control of Staphylococcusorganisms.

Current trends in the compounding of synthetic phenolic germicides havebeen toward the preparation of liquid water-miscible concentratesadapted to be diluted by the ultimate user to prosired concentration. Inthese compositions the phenolic toxicant, e. g. orthophenylphenol, isintimately dispersed or dissolved in materialsadapted to act aemulsifying and solubilizing agents therefor upon subsequent dilutionwith water. A representative composition might compriseorthophenyl-phenol in mixture with an alkali metal hydroxide, a soap orsynthetic wetting and dispersing agent, and a water-miscible organicsolvent, or such combination of two or more of the foregoing as isrequired to give a liquid germi- 'duce aqueous solutions and dispersionsof any detained which have the desirable properties of the knownmixtures as regards stability and water miscibility and in which thetoxicity of the phenolic constituent (as measured in terms of phenolcoeflicient against Staph. aureus) is much higher than might be expectedfrom a knowledge of the toxicities of the components of the composition.The amount of pine oil or alpha-terpineol which is incorporated in suchcomposition is generally between about 0.25 and 4 parts per part byweight of orthophenylphenol in the composition. In mixtures of theseproportions, the apparent phenol coeflicient of the orthophenylphenol isappreciably in excess of that of orthophenylph'enol in unmodifiedcompositions, and more than additive with respect to the sum total ofthe efficiencies of the phenol, soap, and pine oil or alphaterpineolpresent in the mixture. The criticality of the foregoing proportion isevidenced by a substantial lowering of the apparent phenol coefficientof the orthophenylphenol in compositions wherein more or less than therecommended amount of the pine oil or alpha-terpineol is used.

The preferred proportion of pine oil or alphaterpineol varies with theparticular soap or other wetting agent and the amounts thereof employedin the composition. When vegetable oil soaps are a major component ofthe mixture, from 0.5 to 3.0 parts thereof, and from 0.25 to 3.0 partsof the pine oil or alpha-terpineol per part by weight oforthophenylphenol constitutes the preferred proportion range. With(partially neutralized sulfonat'ed vegetable oils such as castor oil,olive oil, linseed oil, etc., best results are obtained with from 0.3 to2.5 parts of pine oil or alpha-terpineol in combination with 0.25 to 2.0parts of the sulfonated product per part by weight of orthophenylphenol.In compositions including a synthetic emulsifying and detergent agentsuch as an alkali metal salt of a sulfated higher alcohol or aromaticsulfonic acid, a mixture of from 0.5 to 4.0 parts each of theemulsifying and detergent agent and pine oil or alpha-terpineol sperpart by weight of orthophenylphenol is most satisfactory. In any eventsubstantial excesses of soap, synthetic emulsifyin agent, and pine oilor alphaterpineol are to be avoided if compositions of higheffectiveness against Staphylococcus organisms are to be obtained.

In operating according to the invention, it is sumcient to add therequired amount of pine oil or alpha-terpineol to the water-misciblegermicidal concentrate with stirring. In an alternate procedure, theorthophenylphenol may be disphenol, and does not occur when many otherphenolic materials are substituted therefor. Representative of thephenols which are not operable in accordance with the present inventionare parachlorothymol, monochloroorthophenyl phenol andmonochloroparaphenylphenol. While mixtures of these phenols with pineoil have a somewhat increased effectiveness against -E. typhi, theireffectiveness against the more difficuitly controlled Staphylococcusorganisms does not appear to be affected.

The method employed in determining the phenol coeflicients set forth inthe following examples is the one developed by the United States PublicHealth Service, Hygienic Laboratory, and described in Circular #198 ofthe Food and Dru Administration, United States Department ofAgriculture. These values are based upon a coefficient of 1.0 for purephenol. The phenol c eflicient of orthophenylphenol against Staph.aureus at 20 C. is 14 according to this method.

The following examples are not to be construed as limiting.

EXAMPLE 1 Mixtures of orthophenylphenol, alpha-terpineol, 40 per centpotassium cocoanut-oil soap, and isopropanol were prepared by mixing theseveral ingredients together with warming and stirring. The mixtureswere then cooled 'and tested against Staph. aureus at 20 C. to determinethe apparent phenol coefncient of the orthophenylphenol in each mixture.The following is representative of the results obtained:

Table I Parts by weight b Apparentp enol Peres tb wei ht OrthmAlphamogmpgnol 8x331 2139?- phenyiterpin- :3? composition phenol phenoleol p 1 l 3 9.1 42.3. 1 2 a 8.7 60. 1 3 5.5 7.3 60. l 0 3 10.2 (plus 8%31. 1.

sodium hydroxide). O l 2.6 10 (plus 6% so- Lessthan 0.5.

$13111 hydrox-' 1 Phenol coefficient for alpha-terpineol soap mixture.

Alpha-terpineol alone was found to have substantially no effect uponStaph. aureus.

, solved or dispersed in the pine oil or terpineol or Exunmla Table I!PM by Wei! Per cent by Apparent weight phenol ooom E 1 1 5;33 oi fi t ms ycom 7 Pm ing agent tion phenol 1 0. s 0. s 20 1 1 0. 0 1a 7 33 1 2 1$0 43 1 a 1. 0 1s. a 1 4 2 1a 2 n M Santomerse #3 alone was found tohave substantially no effect upon Staph. aureus.

Exsmm: 3

In a similar manner orthophenylphenol was compounded with pine oil and apartially neutralized sulfonated castor oil marketed as Nopco. In thisoperation, the pine oil and sulfonated castor oil product were mixedtogether and in- -eorporated with orthophenylphenol and sufficientisopropanol to give a stable liquid concentrate. The following tablesets forth the proportions of constituents employed and resultsobtained.

. Table III Parts by weight per each of ortho- Apparent phenylphenolphenol ooefllcient of orthophenylphenol Sulionated against Sapl. Pineoil oastor oil aumu product 1.07 0.43 as 0.0 0.0 45 0.0 1.0 21 0.3 1.2is 1.00 0.34 20 1.2; 0.17 as 65 0.3 1.2 as 0.0 1.0 10 2.00 0.42 40 1.700.71 00 1.20 1.20 30 1.0 10 31 2'3 it t 1104 1110 30 Combinations ofpine oil with the sulfonated a castor oil product in various proportionswere 5 found substantially without effect in the control of Staph.aureus.

Exsslru: 4

7 Mixtures of orthophenylphenol, pine oil, and

40 per cent potassium cocoanut-oil soap were prepared substantially asdescribed in Example 1.

2,359,941 3 Table IV rem by weight Percent by Percent by Percent byApparent phenol weight of sodiweight of isoweight oi coefficient ofOrtho- 407 um hydroxide propanol in water in orthophmylphcnyl Pine oilin compofltion composition composition phenol pheno l 3 2. 0 l0. 2 0. 13i. 4

l 0. 3 l. 9 ll. 43 5. 7 40. 0

l 2. 5 10 ll 39 l I. 5 l5 9. 8 37 The mixture of oil and soap was foundto be 2 not effective against Staph. aureus.

Exams: 5

Potassium linseed oil soap was substituted for potassium'cocoanut oilsoap as shown in the preceding example. The following table sets forthrepresentative results obtained.

I claim:

1. A water-miscible liquid germicidal concentrate includingorthophenylphenol dispersed therein as the principal toxic ingredientand from 0.25 to 4 parts of a material selected from the 0 classconsisting of pine oil and alpha-terpinecl per part by weight oforthophenylphenoL 2. A water-miscible liquid germicidal concen- Table VParts by weight Apparent phenol Percent by Percent by Percent bycoeiilcient oi wei t of sodiweight of isoweight oi orthobhenyl- Ortho-407 um ydraxide prcpanol in water in pheno against phenyb Pine oil incomposition composition composition Staph. cumu phenol p at 21 C.

l 0 3 2. 0 l0. 2 6. 1 29. 6 l 0. 26 3 1. 94 9. 7 5. 85 33. 3 l l 3 1. 78. 47 6. (B 42. 6 1 2 3 1. 45 7. 25 4. 36 37. 9 l 3 4 1. l3 5. 62 3. 3732 The germicidal concentrates as set forth in the foregoing examplesare diluted with water to obtain aqueous bactericidal mixtures of goodstability and adapted to be employed as household disinfectants. Theaqueous mixtures are also suitable for use in hospital and clinical workand may be applied to any surface upon which it is desired to controlStaphylococcus organisms and particularly Staph. aureus. Likewise, theymay be employed for the control of other organisms such as E; tvphi, andthe like.

In place of isopropanol as shown in certain of the foregoing examples,other water-miscible organic solvents may be employed, e. g. ethanol,acetone, ethylene glycol, ethylene glycol acetate. ethoxy-ethanol,methoiw-ethanol, etc. Similarly, potassium hydroxide may be substitutedfor sodium hydroxide. Other wetting and emulsifying agents and soapswhich may be incorporated into the disclosed compositions include sodiumlauryl sulfate, potassium lauryl sulfate, sodium decyl sulfate, sodiumsalts of sulfonated alkylphenylphenols, partialLv neutralized sulfatedcocoanut oil. sodium oleate, potassium palmitate, etc. Alkaline reactingdetergents such as sodium pyrophosphate, potassium pyrophosphate, sodiumhexametaphosphate, and the like are-also compatible with theorthophenylphenol containing compositions. Similarly dyes, perfumes, andthe like may be incorporated therein.

trate including orthophenylphenol dispersed therein as the principaltoxic ingredient and from 0.25 to 4 parts of pine oil orthophenylphenol.

3. A water-nuscible liquid germicidal concentrate includingorthophenylphenol dispersed therein as the principal toxic ingredientand from 0.25 to 4 parts of aipha-terpineol per part by weight oforthophenylphenol 4. An aqueous germicidal composition includingorthophenylphenol dispersed therein as the principal toxic ingredientand from 0.25 to 4 parts of a material selected from the class consisting of pine oil and alpha-terpineol per part by weight oforthophenylphenol.

5. A water-miscible liquid germicidal concentrate includingorthophenylphenol dispersed per partby weight of 0 therein as theprincipal toxic ingredient, from 0.3

to 2.5 parts of pine oil, and from 0.25 to 2.0 parts of a partiallyneutralized sulfonated vegetable oil per part by weight oforthophenylphenol.

6. A water-miscible liquid germicidal concentrate includingorthophenylphenol dispersed.

therein as the principal toxic ingredient, from 0.25 to 3.0 parts ofpine oil, and from 0.5 to 3.0 parts of a vegetable oil soap per part byweight of orthophenylphenol.

7. A water-miscible liquid germicidal concentrate includingorthophenylphenol dispersed therein as the principal toxic ingredient,from 0.25 to 3.0 parts of pine oil, and from 0.5 to 3.0 parts of coconutoil soap per part by weight of orthophenylphenol. I

8. A water-miscible liquid germicidal concentrate includingorthophenylphenol dispersed therein as the principal toxic ingredient,from 0.5 to 4 parts of pine oil, and from 0.5 to 4 parts of a,

synthetic emulsifying and detergent agent eelected from the classconsisting of the alkali metsl 'salts of sulfated higher alcohols andaromatic sulfonic acids per part by weight of orthophenyla phenol.

ALEXANDER M. PARTANSKY.

